CA2414411C - Silylated polyurethanes for adhesives and sealants with improved mechanical properties - Google Patents
Silylated polyurethanes for adhesives and sealants with improved mechanical properties Download PDFInfo
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- CA2414411C CA2414411C CA2414411A CA2414411A CA2414411C CA 2414411 C CA2414411 C CA 2414411C CA 2414411 A CA2414411 A CA 2414411A CA 2414411 A CA2414411 A CA 2414411A CA 2414411 C CA2414411 C CA 2414411C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S528/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S528/905—Polymer prepared from isocyanate reactant has adhesive property
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Sealing Material Composition (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The silylated polyurethane polymer includes a polyurethane prepolymer having between greater than about 50 to about 95 % of NCO groups terminated with silane capping agents. The polymer has an improved mechanical properties. The polymer can also have between about 5 % to less than about 50 % of the NCO groups terminated with low molecular weight terminators.
Description
SILYLATED POLYURETHANES FOR ADHESIVES AND
SEALANTS WITH IMPROVED MECHANICAL PROPERTIES
This invention relates generally to silylated polyurethane polymers, and more particularly to silane-terminated polyurethane polymers with improved mechanical properties, to silane- and low molecular weight terminator-terminated polyurethane polymers, to sealant compositions containing such polymers, and to methods of making them.
Generally, conventional urethane-based adhesives and sealants have better physical properties, including tensile strength, elongation, and tear strength, than do adhesives and sealants made with silylated polyurethane capped with common capping agents such as aminotrimethoxysilanes and isocyanatotrimethoxysilanes. This makes it difficult to use silylated polyurethane-based adhesives and sealants in some applications, despite other advantages that they have over urethane-based products.
There are currently two approaches used to improve the mechanical properties of silylated polyurethanes. One solution has been to cap the polyurethane completely using difunctional silanes as capping agents. However, the cure rate of adhesives and sealants made with this type of silylated polyurethane decreases unacceptably in some cases. The other approach is to cap the polyurethane completely using certain special capping agents which reduce the cross-linking density. These include silanes having the general formulation HNR' Si(OCH3)31 such as N-phenyl-gamma-aminopropyltrimethoxysilane. These special silanes are costly to use because of their high prices and high molecular weights, and the improvement in properties they provide is limited.
U.S. Patent No. 3,627,722 (Seiter) discloses a partially capped polyurethane sealant composition. Seiter states that between 5 and 50% of the NCO groups should be capped. According to Seiter, capping more than 50% of the NCO groups produces a soft polymer with less cohesive strength than when less than 50% are capped.
Therefore, there is a need for economical silylated polyurethanes with improved mechanical properties for use in adhesives and sealants.
This need is met by the present invention which provides a novel silylated polyurethane polymer having improved mechanical properties which can be used in sealant compositions, and a method of making the same.
The silylated polyurethane polymer includes a polyurethane pre-polymer having between greater than about 50 to about 95% of the NCO groups terminated with silane groups. The polymer has improved mechanical properties, including tensile strength, elongation, and tear strength. The polymer can also have between about 5% to less than about 50% of the NCO groups terminated with low molecular weight terminators. Low molecular weight terminators include an active hydrogen which can react with the NCO groups.
The silane groups are preferably selected from HNRSi(OR')31 HSRSi(OR')3, or mixtures thereof, where R represents a divalent organic moiety, R' represents a Cl-, alkyl group, and R2 represents hydrogen, a C1_6 organic moiety, or a second RSi(OR')3 which may be the same as or different from the first such group.
The low molecular weight terminators have groups preferably selected from functional end groups except NCO groups, and inert end groups. The inert end groups are preferably selected from R3OH, R3NH, and R3SH
I
where R3 represents an organic moiety whose molecular weight is less than 1000, and R4 represents hydrogen or R3. The molecular weight of R3 is more preferably less than 100, and R3 is most preferably a methyl, ethyl, or propyl group.
SEALANTS WITH IMPROVED MECHANICAL PROPERTIES
This invention relates generally to silylated polyurethane polymers, and more particularly to silane-terminated polyurethane polymers with improved mechanical properties, to silane- and low molecular weight terminator-terminated polyurethane polymers, to sealant compositions containing such polymers, and to methods of making them.
Generally, conventional urethane-based adhesives and sealants have better physical properties, including tensile strength, elongation, and tear strength, than do adhesives and sealants made with silylated polyurethane capped with common capping agents such as aminotrimethoxysilanes and isocyanatotrimethoxysilanes. This makes it difficult to use silylated polyurethane-based adhesives and sealants in some applications, despite other advantages that they have over urethane-based products.
There are currently two approaches used to improve the mechanical properties of silylated polyurethanes. One solution has been to cap the polyurethane completely using difunctional silanes as capping agents. However, the cure rate of adhesives and sealants made with this type of silylated polyurethane decreases unacceptably in some cases. The other approach is to cap the polyurethane completely using certain special capping agents which reduce the cross-linking density. These include silanes having the general formulation HNR' Si(OCH3)31 such as N-phenyl-gamma-aminopropyltrimethoxysilane. These special silanes are costly to use because of their high prices and high molecular weights, and the improvement in properties they provide is limited.
U.S. Patent No. 3,627,722 (Seiter) discloses a partially capped polyurethane sealant composition. Seiter states that between 5 and 50% of the NCO groups should be capped. According to Seiter, capping more than 50% of the NCO groups produces a soft polymer with less cohesive strength than when less than 50% are capped.
Therefore, there is a need for economical silylated polyurethanes with improved mechanical properties for use in adhesives and sealants.
This need is met by the present invention which provides a novel silylated polyurethane polymer having improved mechanical properties which can be used in sealant compositions, and a method of making the same.
The silylated polyurethane polymer includes a polyurethane pre-polymer having between greater than about 50 to about 95% of the NCO groups terminated with silane groups. The polymer has improved mechanical properties, including tensile strength, elongation, and tear strength. The polymer can also have between about 5% to less than about 50% of the NCO groups terminated with low molecular weight terminators. Low molecular weight terminators include an active hydrogen which can react with the NCO groups.
The silane groups are preferably selected from HNRSi(OR')31 HSRSi(OR')3, or mixtures thereof, where R represents a divalent organic moiety, R' represents a Cl-, alkyl group, and R2 represents hydrogen, a C1_6 organic moiety, or a second RSi(OR')3 which may be the same as or different from the first such group.
The low molecular weight terminators have groups preferably selected from functional end groups except NCO groups, and inert end groups. The inert end groups are preferably selected from R3OH, R3NH, and R3SH
I
where R3 represents an organic moiety whose molecular weight is less than 1000, and R4 represents hydrogen or R3. The molecular weight of R3 is more preferably less than 100, and R3 is most preferably a methyl, ethyl, or propyl group.
The functional end groups are preferably selected from ZR5OH, ZR5NH, and ZRSSH, where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000, R5 represents a divalent organic moiety, and Z represents any functional group except NCO groups. The molecular weight of R4 is more preferably less than 100, and most preferably R4 is a methyl, ethyl, or propyl group.
Z is preferably selected from -NH, -CH-CH21 -SH, -OH, and -CH=CH2.
\ /
where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000, and more preferably less than 100. R4 is most preferably a methyl, ethyl, or propyl group.
Another aspect of the invention are sealant and adhesive compositions including the silylated polyurethane polymer as described above. The sealant and adhesive compositions will typically include additional compounds, such as fillers, reinforcing agents, solvents, catalysts, rheology modifiers, ultraviolet light screening compounds, and adhesion promoters.
Another aspect of the invention is a method of making the silylated polyurethane polymer described above. The method includes reacting a polyurethane prepolymer having NCO groups with silane capping agents so that between greater than about 50 to about 95% of the NCO groups are terminated with silane groups.
The method optionally includes reacting the polyurethane prepolymer with a low molecular weight terminator so that between about 5 to less than about 50% of the NCO groups are terminated with low molecular weight terminators.
Preparation of isocyanate terminated urethane prepolymers, and silylated polyurethane with silane capping agents, are well known in the art. See, e.g., U.S. Patent Nos. 3,627,722, 3,632,557, 3,979,344, and 4,222,925.
Curing of the polymer results from hydrolysis of the silane end groups and condensation of Si-OH moieties.
Z is preferably selected from -NH, -CH-CH21 -SH, -OH, and -CH=CH2.
\ /
where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000, and more preferably less than 100. R4 is most preferably a methyl, ethyl, or propyl group.
Another aspect of the invention are sealant and adhesive compositions including the silylated polyurethane polymer as described above. The sealant and adhesive compositions will typically include additional compounds, such as fillers, reinforcing agents, solvents, catalysts, rheology modifiers, ultraviolet light screening compounds, and adhesion promoters.
Another aspect of the invention is a method of making the silylated polyurethane polymer described above. The method includes reacting a polyurethane prepolymer having NCO groups with silane capping agents so that between greater than about 50 to about 95% of the NCO groups are terminated with silane groups.
The method optionally includes reacting the polyurethane prepolymer with a low molecular weight terminator so that between about 5 to less than about 50% of the NCO groups are terminated with low molecular weight terminators.
Preparation of isocyanate terminated urethane prepolymers, and silylated polyurethane with silane capping agents, are well known in the art. See, e.g., U.S. Patent Nos. 3,627,722, 3,632,557, 3,979,344, and 4,222,925.
Curing of the polymer results from hydrolysis of the silane end groups and condensation of Si-OH moieties.
In the present invention, a majority of NCO groups are capped with common silane capping agents. The remaining NCO groups are either left unreacted, or are capped with low molecular weight terminators. The low molecular weight terminators can form inert end groups or introduce different functional groups into the silylated polyurethane.
Between greater than about 50 to 95%, preferably between about 80 to about 95%, of the NCO groups can be capped with common suitable silane capping agents. There can be between about 5 to less than about 50%, preferably about 5 to about 20%, uncapped NCO groups. The percentage of capped NCO groups depends on the chemical structure of the isocyanate terminated urethane prepolymer. That is, it depends on factors including the type of raw materials, such as TDI or MDI and polyester polyols or polyether polyols, functionality, molecular weights, and also on the desired end use for the polymer.
Suitable silanes include, but are not limited to, silanes having the following general formulas:
HNRSi(OR')31 HSRSi(OR1)31 or mixtures thereof, I
where R represents a divalent organic moiety, R' represents a C1_6 alkyl group, and R2 represents hydrogen, a Cl-,, organic moiety, or a second RSi(OR1)3 which may be the same as or different from the first such group.
The portion of the NCO groups which are not capped with the silane may optionally be capped with low molecular weight terminators. Generally, the low molecular weight terminators can be any substance containing hydrogen which will react with an NCO group. The low molecular weight terminators can form inert end groups or introduce desirable functional groups onto the polymers.
Low molecular weight terminators which form inert end groups include, but are not limited to, the following:
R3OH, R3NH, and R3SH
where R3 represents an organic moiety whose molecular weight is less than 1000, preferably less than 100, and most preferably R3 is a methyl, ethyl, or propyl group, and R4 represents hydrogen or R3. Low molecular weight terminators which can be used to introduce different functional groups include, but are not limited to, ZR5OH, ZR5NH, and ZR5SH, where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000, R5 represents a divalent organic moiety, and Z represents any functional group except NCO
groups. The functional groups include, but are not limited to, -NH, -CH-CH2, -SH, -OH, and -CH=CH2 \ /
where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000.
The silane capping agents and the low molecular weight terminators can be added together or separately. The sequence in which the reactants are added depends on their relative reactivity.
Adhesives and sealants made using the polyurethane prepolymers of the present invention will typically include fillers such as carbon black, and catalysts such as dibutyltin diacetate. Other fillers and catalysts can also be used.
The adhesives and sealants can also contain additional components including adhesion promoters, rheology modifiers, and ultraviolet light screening compounds, and other components if desired.
In order that the invention may be more readily understood, reference is made to the following non-limiting examples.
Example 1. A partially capped silylated polyurethane 1179.58 g of 2000 molecular weight polyether diol (PPG-2200 from ARCO
Chemical Company), 123.14 g of TDI (80/20 isomer mixture) and 96.41 g of anhydrous toluene were charged. The reaction was carried out at 140 F in the presence of 0.58 g of dibutyltin diacetate (METACURE T-1 from Air Products and Chemical, Inc.) and 0.29 g of acetic acid under anhydrous condition. When the NCO percentage dropped to 0.708 in about 2 hours, 36.58 g of gamma-aminopropyltrimethoxysilane (Silquest A-1110 from OSi) was added after the temperature had been cooled down to 110 F. Then, the NCO percentage dropped to 0.106 in about 15 min. This partially capped silylated polyurethane had 15% uncapped NCO groups.
Example 2. A silylated polyurethane fully capped with a silane capping agent and a low molecular weight terminator 1179.58 g of 2000 molecular weight polyether diol (PPG-2200 from ARCO
Chemical Company), 123.14 g of TDI (80/20 isomer mixture) and 96.41 g of anhydrous toluene were charged. The reaction was carried out at 140 F in the presence of 0.58 g of dibutyltin diacetate (METACURE T-1 from Air Products and Chemical, Inc.) and 0.29 g of acetic acid under anhydrous condition. When the NCO percentage dropped to 0.708 in about 2 hours, 36.58 g of gamma-aminopropyltrimethoxysilane (Silquest A-1110 from OSi) and 1.12 g of methanol were added when the temperature had been cooled down to 110 F. Then, the NCO percentage dropped to zero in less than 30 min. The reaction was done.
Example 3. Comparison of properties of adhesives made with the silylated polyurethane of Example 2 and a silylated polyurethane fully capped with Silquest A-1110 Adhesives were made using the silylated polyurethane of Example 2 and a silylated polyurethane fully capped with Silquest A-1110. The only difference between these two silylated polyurethanes is the capping agent. The adhesive formulation is as follows:
Adhesive Formula Ingredient Part by wt.
Silylated polyurethane 634.14 Carbon blacks 300.00 Methanol, anhydrous 57.00 Dibutyltin diacetateb 1.00 Neoalkoxy, tri(Nethylaminoethylamino) titanatec 3.36 N-beta-(Aminoethyl)-gamma-aminopropyltrimethoxysilaned 4.50 a. Regal 300R from Cabot Corporation b. METACURE T-1 from Air Products and Chemical, Inc.
c. KEN-REACT Lica 44U
d. Silquest A-1120 Comparison of Properties of Silylated Polyurethane Adhesives Property Adhesive A a Adhesive B b Tack-free time @23 C/50% RH, min. 12 12 Cure rate @23 C/50% RH, in/24 h 0.24 0.24 Tensile strength @ break, PSI C 1400 1000 Tear strength, PLI C 207 150 Elongation @ break, % C 400 200 Hardness, Shore A 60 72 Adhesion to glass w/o primer 100 % CF d 100 % CF d a. Adhesive A was made with the silylated polyurethane of Example 2.
b. Adhesive B was made with the silylated polyurethane which was prepared from identical prepolymer in Example 2 but fully capped with Silquest A-1110.
c. Samples were cured for 6 days in 23 C/50% RH environment chamber.
d. CF stands for cohesive failure.
The silylated polyurethane of Example 2 (fully capped with a silane capping agent and a low molecular weight terminator) had improved tensile strength, tear strength, and elongation as compared to the silylated polyurethane fully capped with a silane capping agent. The tack-free time and the cure rate for the two adhesives are the same. Thus, the silylated polyurethane of the present invention provides improved properties without sacrificing cure rate. In addition, the present invention makes silylated polyurethane more tailorable and offers more flexibility to formulate adhesives and sealants. Furthermore, the cost of making this type of silylated polyurethane can be lower than that of normal silylated polyurethane.
While certain representative embodiments and details have been shown for purposes of illustrating the invention, it will be apparent to those skilled in the art that various changes in the methods and apparatus disclosed herein may be made without departing from the scope of the invention, which is defined in the appended claims.
Between greater than about 50 to 95%, preferably between about 80 to about 95%, of the NCO groups can be capped with common suitable silane capping agents. There can be between about 5 to less than about 50%, preferably about 5 to about 20%, uncapped NCO groups. The percentage of capped NCO groups depends on the chemical structure of the isocyanate terminated urethane prepolymer. That is, it depends on factors including the type of raw materials, such as TDI or MDI and polyester polyols or polyether polyols, functionality, molecular weights, and also on the desired end use for the polymer.
Suitable silanes include, but are not limited to, silanes having the following general formulas:
HNRSi(OR')31 HSRSi(OR1)31 or mixtures thereof, I
where R represents a divalent organic moiety, R' represents a C1_6 alkyl group, and R2 represents hydrogen, a Cl-,, organic moiety, or a second RSi(OR1)3 which may be the same as or different from the first such group.
The portion of the NCO groups which are not capped with the silane may optionally be capped with low molecular weight terminators. Generally, the low molecular weight terminators can be any substance containing hydrogen which will react with an NCO group. The low molecular weight terminators can form inert end groups or introduce desirable functional groups onto the polymers.
Low molecular weight terminators which form inert end groups include, but are not limited to, the following:
R3OH, R3NH, and R3SH
where R3 represents an organic moiety whose molecular weight is less than 1000, preferably less than 100, and most preferably R3 is a methyl, ethyl, or propyl group, and R4 represents hydrogen or R3. Low molecular weight terminators which can be used to introduce different functional groups include, but are not limited to, ZR5OH, ZR5NH, and ZR5SH, where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000, R5 represents a divalent organic moiety, and Z represents any functional group except NCO
groups. The functional groups include, but are not limited to, -NH, -CH-CH2, -SH, -OH, and -CH=CH2 \ /
where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000.
The silane capping agents and the low molecular weight terminators can be added together or separately. The sequence in which the reactants are added depends on their relative reactivity.
Adhesives and sealants made using the polyurethane prepolymers of the present invention will typically include fillers such as carbon black, and catalysts such as dibutyltin diacetate. Other fillers and catalysts can also be used.
The adhesives and sealants can also contain additional components including adhesion promoters, rheology modifiers, and ultraviolet light screening compounds, and other components if desired.
In order that the invention may be more readily understood, reference is made to the following non-limiting examples.
Example 1. A partially capped silylated polyurethane 1179.58 g of 2000 molecular weight polyether diol (PPG-2200 from ARCO
Chemical Company), 123.14 g of TDI (80/20 isomer mixture) and 96.41 g of anhydrous toluene were charged. The reaction was carried out at 140 F in the presence of 0.58 g of dibutyltin diacetate (METACURE T-1 from Air Products and Chemical, Inc.) and 0.29 g of acetic acid under anhydrous condition. When the NCO percentage dropped to 0.708 in about 2 hours, 36.58 g of gamma-aminopropyltrimethoxysilane (Silquest A-1110 from OSi) was added after the temperature had been cooled down to 110 F. Then, the NCO percentage dropped to 0.106 in about 15 min. This partially capped silylated polyurethane had 15% uncapped NCO groups.
Example 2. A silylated polyurethane fully capped with a silane capping agent and a low molecular weight terminator 1179.58 g of 2000 molecular weight polyether diol (PPG-2200 from ARCO
Chemical Company), 123.14 g of TDI (80/20 isomer mixture) and 96.41 g of anhydrous toluene were charged. The reaction was carried out at 140 F in the presence of 0.58 g of dibutyltin diacetate (METACURE T-1 from Air Products and Chemical, Inc.) and 0.29 g of acetic acid under anhydrous condition. When the NCO percentage dropped to 0.708 in about 2 hours, 36.58 g of gamma-aminopropyltrimethoxysilane (Silquest A-1110 from OSi) and 1.12 g of methanol were added when the temperature had been cooled down to 110 F. Then, the NCO percentage dropped to zero in less than 30 min. The reaction was done.
Example 3. Comparison of properties of adhesives made with the silylated polyurethane of Example 2 and a silylated polyurethane fully capped with Silquest A-1110 Adhesives were made using the silylated polyurethane of Example 2 and a silylated polyurethane fully capped with Silquest A-1110. The only difference between these two silylated polyurethanes is the capping agent. The adhesive formulation is as follows:
Adhesive Formula Ingredient Part by wt.
Silylated polyurethane 634.14 Carbon blacks 300.00 Methanol, anhydrous 57.00 Dibutyltin diacetateb 1.00 Neoalkoxy, tri(Nethylaminoethylamino) titanatec 3.36 N-beta-(Aminoethyl)-gamma-aminopropyltrimethoxysilaned 4.50 a. Regal 300R from Cabot Corporation b. METACURE T-1 from Air Products and Chemical, Inc.
c. KEN-REACT Lica 44U
d. Silquest A-1120 Comparison of Properties of Silylated Polyurethane Adhesives Property Adhesive A a Adhesive B b Tack-free time @23 C/50% RH, min. 12 12 Cure rate @23 C/50% RH, in/24 h 0.24 0.24 Tensile strength @ break, PSI C 1400 1000 Tear strength, PLI C 207 150 Elongation @ break, % C 400 200 Hardness, Shore A 60 72 Adhesion to glass w/o primer 100 % CF d 100 % CF d a. Adhesive A was made with the silylated polyurethane of Example 2.
b. Adhesive B was made with the silylated polyurethane which was prepared from identical prepolymer in Example 2 but fully capped with Silquest A-1110.
c. Samples were cured for 6 days in 23 C/50% RH environment chamber.
d. CF stands for cohesive failure.
The silylated polyurethane of Example 2 (fully capped with a silane capping agent and a low molecular weight terminator) had improved tensile strength, tear strength, and elongation as compared to the silylated polyurethane fully capped with a silane capping agent. The tack-free time and the cure rate for the two adhesives are the same. Thus, the silylated polyurethane of the present invention provides improved properties without sacrificing cure rate. In addition, the present invention makes silylated polyurethane more tailorable and offers more flexibility to formulate adhesives and sealants. Furthermore, the cost of making this type of silylated polyurethane can be lower than that of normal silylated polyurethane.
While certain representative embodiments and details have been shown for purposes of illustrating the invention, it will be apparent to those skilled in the art that various changes in the methods and apparatus disclosed herein may be made without departing from the scope of the invention, which is defined in the appended claims.
Claims (71)
1. A silylated polyurethane polymer comprising:
a polyurethane prepolymer having between greater than about 80 to about 95% of NCO groups terminated with silane capping agents, the polyurethane prepolymer being cured to form the silylated polyurethane polymer and the silylated polyurethane polymer having improved mechanical properties.
a polyurethane prepolymer having between greater than about 80 to about 95% of NCO groups terminated with silane capping agents, the polyurethane prepolymer being cured to form the silylated polyurethane polymer and the silylated polyurethane polymer having improved mechanical properties.
2. The silylated polyurethane polymer of claim 1 wherein the silane capping agents are selected from HSRSi(OR1)3 or mixtures thereof, where R represents a divalent organic moiety, R1 represents a C1-6 alkyl group, R2 represents hydrogen or C1-6 organic moiety or a second RSi(OR1)3 which may be the same as or different from a first RSi(OR1)3 group in the silane capping agent.
3. The silylated polyurethane polymer of claim 1 wherein between about 5% to less than about 20% of the NCO groups are terminated with low molecular weight terminators, wherein the low molecular weight terminators include an active hydrogen which reacts with the NCO groups to terminate the NCO groups with the low moleular weight terminators.
4. The silylated polyurethane polymer of claim 3 wherein the low molecular weight terminators have a group selected from functional end groups except NCO groups and inert end groups.
5. The silylated polyurethane polymer of claim 4 wherein the low molecular weight terminators having inert end groups are selected from R3OH, , and R3SH
where R3 represents an organic moiety whose molecular weight is less than 1000, and R4 represents hydrogen or R3.
where R3 represents an organic moiety whose molecular weight is less than 1000, and R4 represents hydrogen or R3.
6. The silylated polyurethane polymer of claim 5 wherein the molecular weight of R3 is less than 100.
7. The silylated polyurethane polymer of claim 5 wherein R3 is selected from methyl, ethyl, and propyl.
8. The silylated polyurethane polymer of claim 4 wherein the low molecular weight terminators having functional end groups are selected from ZR5OH, , and ZR5SH, where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000, R5 represents a divalent organic moiety, and Z represents any functional group except NCO groups.
9. The silylated polyurethane polymer of claim 8 wherein Z is selected from , -SH, -OH, and -CH=CH2.
where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000.
where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000.
10. A method of making a silylated polyurethane polymer comprising;
reacting a polyurethane prepolymer having NCO groups with silane capping agents so that between greater than about 80 to about 95% of the NCO groups are terminated with silane capping agents.
reacting a polyurethane prepolymer having NCO groups with silane capping agents so that between greater than about 80 to about 95% of the NCO groups are terminated with silane capping agents.
11. The method of claim 10 wherein the silane capping agents are selected from , HSRSi(OR1) 3 or mixtures thereof, where R represents a dlvalent organic molety, R1 represents a C1-8 alkyl group, R2 represents hydrogen or C1-6 organic moiety or a second RSi(OR1) 3 which may be the same as or different from a first RSi(OR1) 3 group in the silane capping agent.
12. The method of claim 10 further comprising reacting the polyurethane prepolymer with low molecular weight terminators, wherein the low molecular weight terminators include an active hydrogen which can react with the NCO groups so that between about 5 to less than about 20% of the NCO groups are terminated with low molecular weight terminators.
13. The method of claim 12 wherein the low molecular weight terminators have a group selected from functional end groups except NCO groups and inert end groups.
14. The method of claim 13 wherein the low molecular weight terminators having inert end groups are selected from R3OH, , and R3SH
where RI represents an organic moiety whose molecular weight is less than 1000, and R4 represents hydrogen or R3.
where RI represents an organic moiety whose molecular weight is less than 1000, and R4 represents hydrogen or R3.
15. The method of claim 12 wherein the low molecular weight terminators having functional end groups are selected from ZR5OH, , and ZR5SH, where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000, R5 represents a divalent organic moiety, and Z represents any functional group except NCO groups.
16. The method of claim 15 wherein Z is selected from , -SH, -OH, and -CH=CH2.
where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000.
where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000.
17. The silylated polyurethane polymer of claim 8 wherein the molecular weight of R4 is less than 100.
18. The silylated polyurethane polymer of claim 8 wherein R4 is selected from methyl, ethyl, and propyl.
19. The silylated polyurethane polymer of claim 9 wherein the molecular weight of R4 is less than 100.
20. The silylated polyurethane polymer of claim 9 wherein R4 is selected from methyl, ethyl, and propyl.
21. A sealant composition comprising:
a polyurethane prepolymer having between greater than about 80 to about 95% of NCO groups terminated with silane capping agents, and sufficient filler to form a thixotropic paste, the polyurethane prepolymer being cured to form the silylated polyurethane polymer;
and the sealant composition having improved mechanical properties.
a polyurethane prepolymer having between greater than about 80 to about 95% of NCO groups terminated with silane capping agents, and sufficient filler to form a thixotropic paste, the polyurethane prepolymer being cured to form the silylated polyurethane polymer;
and the sealant composition having improved mechanical properties.
22. The sealant composition of claim 21 wherein the silane capping agents are selected from , HSRSi(OR1) 3 or mixtures thereof, where R represents a divalent organic moiety, R1 represents a C1-6alkyl group, R2 represents hydrogen or C1-6 organic moiety or a second RSi(OR1) 3 which may be the same as or different from a first RSi(OR1) 3 group in the silane capping agent.
23. The sealant composition of claim 21 wherein between about 5% to less than about 20% of the NCO groups are terminated with low molecular weight terminators, wherein the low molecular weight terminators include an active hydrogen which reacts with the NCO groups to terminate the NCO groups with the low molecular weight terminators.
24. The sealant composition of claim 23 wherein the low molecular weight terminators have a group selected from functional end groups except NCO groups and inert end groups.
25. The sealant composition of claim 24 wherein the low molecular weight terminators having inert end groups are selected from R3OH, where R3 represents an organic moiety whose molecular weight is less than 1000, and R4 represents hydrogen or R3.
26. The sealant composition of claim 25 wherein the molecular weight of R3 is less than 100.
27. The sealant composition of claim 25 wherein R3 is selected from methyl, ethyl, and propyl.
28. The sealant composition of claim 24 wherein the low molecular weight terminators having functional end groups are selected from ZR5OH, , and ZR5SH, where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000, R5 represents a divalent organic moiety, and Z represents any functional group except NCO groups.
29. The sealant composition of claim 28 wherein the molecular weight of R4 is less than 100.
30. The sealant composition of claim 28 wherein R4 is selected from methyl, ethyl, and propyl.
31. The sealant composition of claim 28 wherein Z is selected from , -SH, -OH, and -CH=CH2.
where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000.
where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000.
32. The sealant composition of claim 31 wherein the molecular weight of R4 is less than 100.
33. The sealant composition of claim 31 wherein R4 is selected from methyl, ethyl, and propyl.
34. A silylated polyurethane polymer comprising:
a polyurethane prepolymer having between greater than about 50 to about 95% of NCO groups terminated with silane capping agents and between about 5% to less than about 50% of NCO
groups terminated with low molecular weight terminators having functional end groups except NCO groups and inert end groups, the polyurethane prepolymer being cured to form the silylated polyurethane polymer;
wherein the silane capping agents are selected from , HSRSi(OR1) 3 or mixtures thereof, where R represents a divalent organic moiety, R1 represents a C1-6 alkyl group, R2 represents hydrogen or C1-6 organic moiety or a second RSi(OR1) 3 which may be the same as or different from a first RSi(OR')3 group in the silane capping agent; and wherein the low molecular weight terminators having inert end groups are selected from R3OH, , and R3SH
where R3 represents an organic moiety whose molecular weight is less than 1000, and R4 represents hydrogen or R3 or the low molecular weight terminators having functional end groups are selected from ZR5OH, , and ZR5SH, where W represents hydrogen or an organic moiety whose molecular weight is less than 1000, R5 represents a divalent organic moiety, and Z represents any functional group except NCO groups.
a polyurethane prepolymer having between greater than about 50 to about 95% of NCO groups terminated with silane capping agents and between about 5% to less than about 50% of NCO
groups terminated with low molecular weight terminators having functional end groups except NCO groups and inert end groups, the polyurethane prepolymer being cured to form the silylated polyurethane polymer;
wherein the silane capping agents are selected from , HSRSi(OR1) 3 or mixtures thereof, where R represents a divalent organic moiety, R1 represents a C1-6 alkyl group, R2 represents hydrogen or C1-6 organic moiety or a second RSi(OR1) 3 which may be the same as or different from a first RSi(OR')3 group in the silane capping agent; and wherein the low molecular weight terminators having inert end groups are selected from R3OH, , and R3SH
where R3 represents an organic moiety whose molecular weight is less than 1000, and R4 represents hydrogen or R3 or the low molecular weight terminators having functional end groups are selected from ZR5OH, , and ZR5SH, where W represents hydrogen or an organic moiety whose molecular weight is less than 1000, R5 represents a divalent organic moiety, and Z represents any functional group except NCO groups.
35. The silylated polyurethane polymer of claim 34 wherein the molecular weight of R3 is less than 100.
36. The silylated polyurethane polymer of claim 34 wherein R3 is selected from methyl, ethyl, and propyl.
37. The silylated polyurethane polymer of claim 34 wherein the molecular weight of R4 is less than 100.
38. The silylated polyurethane polymer of claim 34 wherein R4 is selected from methyl, ethyl, and propyl.
39. The silylated polyurethane polymer of claim 34 wherein between about 80%
to about 95%
of the terminations are made with the silane capping agents and between about 5% to about 20% of the terminations are made with the low molecular weight terminators.
to about 95%
of the terminations are made with the silane capping agents and between about 5% to about 20% of the terminations are made with the low molecular weight terminators.
40. An adhesive composition comprising:
a silylated polyurethane polymer comprising a polyurethane prepolymer having between greater than about 80 to about 95% of NCO groups terminated with silane capping agents, the polyurethane prepolymer being cured to form the silylated polyurethane polymer, the silylated polyurethane polymer having improved mechanical properties;
a filler; and a catalyst.
a silylated polyurethane polymer comprising a polyurethane prepolymer having between greater than about 80 to about 95% of NCO groups terminated with silane capping agents, the polyurethane prepolymer being cured to form the silylated polyurethane polymer, the silylated polyurethane polymer having improved mechanical properties;
a filler; and a catalyst.
41. The adhesive composition of claim 40 wherein the silane capping agents are selected from , HSRSi(OR1) 3 or mixtures thereof, where R represents a divalent organic moiety, R1 represents a C1-6 alkyl group, R2 represents hydrogen or C1-6 organic moiety or a second RSi(OR1) 3 which may be the same as or different from a first RSi(OR1) 3 group in the silane capping agent.
42. The adhesive composition of claim 40 wherein between about 5% to less than about 20%
of the NCO groups are terminated with low molecular weight terminators, wherein the low molecular weight terminators include an active hydrogen which reacts with the NCO groups to terminate the NCO groups with the low molecular weight terminators.
of the NCO groups are terminated with low molecular weight terminators, wherein the low molecular weight terminators include an active hydrogen which reacts with the NCO groups to terminate the NCO groups with the low molecular weight terminators.
43. The adhesive composition of claim 42 wherein the low molecular weight terminators have a group selected from functional end groups except NCO groups and inert end groups.
44. The adhesive composition of claim 43 wherein the low molecular weight terminators having inert end groups are selected from R3OH, , and R3SH
where R3 represents an organic moiety whose molecular weight is less than 1000, and R4 represents hydrogen or R3.
where R3 represents an organic moiety whose molecular weight is less than 1000, and R4 represents hydrogen or R3.
45. The adhesive composition of claim 44 wherein the molecular weight of R3 is less than 100.
46. The adhesive composition of claim 44 wherein R3 is selected from methyl, ethyl, and propyl.
47. The adhesive composition of claim 43 wherein the low molecular weight terminators having functional end groups are selected from ZR5OH, , and ZR5SH, where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000, R5 represents a divalent organic moiety, and Z represents any functional group except NCO groups.
48. The adhesive composition of claim 47 wherein the molecular weight of R4 is less than 100.
49. The adhesive composition of claim 47 wherein R4 is selected from methyl, ethyl, and propyl.
50. The adhesive composition of claim 47 wherein Z is selected from , -SH, -OH, and -CH=CH2.
where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000.
where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000.
51. The adhesive composition of claim 50 wherein the molecular weight of R4 is less than 100.
52. The adhesive composition of claim 50 wherein R4 is selected from methyl, ethyl, and propyl.
53. A sealant composition comprising:
a polyurethane prepolymer having between greater than about 50 to about 95% of NCO groups terminated with silane capping agents; and sufficient filler to form a thixotropic paste, the polyurethane prepolymer being cured to form the silylated polyurethane polymer, the sealant composition having improved mechanical properties;
wherein the silane capping agent comprises HSRSi(OR1) 3 where R represents a divalent organic moiety, and R1 represents a C1-6 alkyl group.
a polyurethane prepolymer having between greater than about 50 to about 95% of NCO groups terminated with silane capping agents; and sufficient filler to form a thixotropic paste, the polyurethane prepolymer being cured to form the silylated polyurethane polymer, the sealant composition having improved mechanical properties;
wherein the silane capping agent comprises HSRSi(OR1) 3 where R represents a divalent organic moiety, and R1 represents a C1-6 alkyl group.
54. The sealant composition of claim 53 wherein the polyurethane prepolymer has between about 80% to about 95% of NCO groups terminated with silane capping agents.
55. A method of making a silylated polyurethane polymer comprising:
reacting a polyurethane prepolymer having NCO groups with silane capping agents so that between greater than about 50 to about 95% of NCO groups are terminated with silane capping agents, wherein the silane capping agents comprise HSRSi(OR1) 3 where R represents a divalent organic moiety, and R1 represents a C1-6 alkyl group.
reacting a polyurethane prepolymer having NCO groups with silane capping agents so that between greater than about 50 to about 95% of NCO groups are terminated with silane capping agents, wherein the silane capping agents comprise HSRSi(OR1) 3 where R represents a divalent organic moiety, and R1 represents a C1-6 alkyl group.
56. The method of claim 55 wherein between about 80% to about 95% of NCO
groups are terminated with silane capping agents.
groups are terminated with silane capping agents.
57. An adhesive composition comprising:
a silylated polyurethane polymer comprising a polyurethane prepolymer having between greater than about 50 to about 95% of NCO groups terminated with silane capping agents, the polyurethane prepolymer being cured to form the silylated polyurethane polymer, the silylated polyurethane polymer having improved mechanical properties;
a filler; and a catalyst;
wherein the silane capping agents comprise HSRSi(OR1) 3 where R represents a divalent organic moiety, and R1 represents a C1-6 alkyl group.
a silylated polyurethane polymer comprising a polyurethane prepolymer having between greater than about 50 to about 95% of NCO groups terminated with silane capping agents, the polyurethane prepolymer being cured to form the silylated polyurethane polymer, the silylated polyurethane polymer having improved mechanical properties;
a filler; and a catalyst;
wherein the silane capping agents comprise HSRSi(OR1) 3 where R represents a divalent organic moiety, and R1 represents a C1-6 alkyl group.
58. The adhesive composition of claim 57 wherein the polyurethane prepolymer has between about 80% to about 95% of NCO groups terminated with silane capping agents.
59. A silylated polyurethane polymer comprising:
a polyurethane prepolymer having between greater than about 50 to about 95% of NCO groups terminated with silane capping agents, the polyurethane prepolymer being cured to form the silylated polyurethane polymer, the silylated polyurethane polymer having improved mechanical properties;
wherein the silane capping agents comprise HSRSi(OR1)3 where R represents a divalent organic moiety, and R1 represents a C1-6 alkyl group.
a polyurethane prepolymer having between greater than about 50 to about 95% of NCO groups terminated with silane capping agents, the polyurethane prepolymer being cured to form the silylated polyurethane polymer, the silylated polyurethane polymer having improved mechanical properties;
wherein the silane capping agents comprise HSRSi(OR1)3 where R represents a divalent organic moiety, and R1 represents a C1-6 alkyl group.
60. The silylated polyurethane polymer of claim 59 wherein the polyurethane prepolymer has between about 80% to about 95% of NCO groups terminated with silane capping agents.
61. The silylated polyurethane polymer of claim 59 wherein between about 5% to less than about 50% of the NCO groups are terminated with low molecular weight terminators, wherein the low molecular weight terminators include an active hydrogen which reacts with the NCO
groups to terminate the NCO groups with the low molecular weight terminators.
groups to terminate the NCO groups with the low molecular weight terminators.
62. The silylated polyurethane polymer of claim 61 wherein the low molecular weight terminators have a group selected from functional end groups except NCO groups and inert end groups.
63. The silylated polyurethane polymer of claim 62 wherein the low molecular weight terminators having inert end groups are selected from R3OH, where R3 represents an organic moiety whose molecular weight is less than 1000, and R4 represents hydrogen or R3.
64. The silylated polyurethane polymer of claim 63 wherein the molecular weight of R3 is less than 100.
65. The silylated polyurethane polymer of claim 63 wherein R3 is selected from methyl, ethyl, and propyl.
66. The silylated polyurethane polymer of claim 62 wherein the low molecular weight terminators having functional end groups are selected from ZR5OH, , and ZR5SH, where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000, R5 represents a divalent organic moiety, and Z represents any functional group except NCO groups.
67. The silylated polyurethane polymer of claim 66 wherein the molecular weight of R4 is less than 100.
68. The silylated polyurethane polymer of claim 66 wherein R4 is selected from methyl, ethyl, and propyl.
69. The silylated polyurethane polymer of claim 66 wherein Z is selected from , -SH, -OH, and -CH=CH2.
where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000.
where R4 represents hydrogen or an organic moiety whose molecular weight is less than 1000.
70. The silylated polyurethane polymer of claim 69 wherein the molecular weight of R4 is less than 100.
71. The silylated polyurethane polymer of claim 69 wherein R4 is selected from methyl, ethyl, and propyl.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/615,921 US6498210B1 (en) | 2000-07-13 | 2000-07-13 | Silylated polyurethanes for adhesives and sealants with improved mechanical properties |
| US09/615,921 | 2000-07-13 | ||
| PCT/US2001/018544 WO2002006367A1 (en) | 2000-07-13 | 2001-06-07 | Silylated polyurethanes for adhesives and sealants with improved mechanical properties |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2414411A1 CA2414411A1 (en) | 2002-01-24 |
| CA2414411C true CA2414411C (en) | 2011-03-08 |
Family
ID=24467324
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2414411A Expired - Fee Related CA2414411C (en) | 2000-07-13 | 2001-06-07 | Silylated polyurethanes for adhesives and sealants with improved mechanical properties |
Country Status (6)
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| US (1) | US6498210B1 (en) |
| AU (1) | AU2001275391A1 (en) |
| BR (1) | BR0112421A (en) |
| CA (1) | CA2414411C (en) |
| MX (1) | MXPA02012908A (en) |
| WO (1) | WO2002006367A1 (en) |
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-
2000
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2001
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- 2001-06-07 MX MXPA02012908A patent/MXPA02012908A/en not_active Application Discontinuation
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| AU2001275391A1 (en) | 2002-01-30 |
| US6498210B1 (en) | 2002-12-24 |
| BR0112421A (en) | 2003-07-08 |
| CA2414411A1 (en) | 2002-01-24 |
| WO2002006367A1 (en) | 2002-01-24 |
| MXPA02012908A (en) | 2003-09-22 |
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Effective date: 20170607 |